EP0755184B1 - Novel pesticide compositions and method of preparation - Google Patents

Novel pesticide compositions and method of preparation Download PDF

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Publication number
EP0755184B1
EP0755184B1 EP95917381A EP95917381A EP0755184B1 EP 0755184 B1 EP0755184 B1 EP 0755184B1 EP 95917381 A EP95917381 A EP 95917381A EP 95917381 A EP95917381 A EP 95917381A EP 0755184 B1 EP0755184 B1 EP 0755184B1
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EP
European Patent Office
Prior art keywords
formulations according
active ingredient
deltamethrin
formulations
pesticide
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EP95917381A
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German (de)
French (fr)
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EP0755184A1 (en
Inventor
Colette Meinard
Jean-Claude Suglia
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Bayer CropScience SA
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Hoechst Schering Agrevo SA
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to new formulations pesticides and their preparation process.
  • the formulations of the invention are presented under the form of a thick paste having the property of being effervescent and to have a microporous structure which gives a very good dispersion in water.
  • This paste can be presented inside a sachet water-soluble plastic, in extruded granules or in platelets. The last two presentations requiring a drying operation.
  • This paste is a composition which has a coefficient very low viscoelasticity, this is not a solution colloidal as a gel, but results from absorption by a solid, a liquid until saturation, the particle size solid particles being between 5 and 40 ⁇ .
  • the active ingredient is in solution in a weak solvent volatile and the emulsifiers contained in this solvent allow preparation to release the active ingredient under form of an emulsion after dilution in water.
  • the formulations of the invention have a structure microporous facilitating their dispersion in water at the time of their use. This structure is obtained by causing a gaseous evolution within the dough at the time of its preparation. The gas is released by the reaction of the generator micropores and the effervescent agent.
  • One of the advantages of the invention is to present formulations such as concentrated suspensions or usually liquid emulsifiable concentrates, under the form a solid or a paste.
  • Another advantage is to avoid any risk of leakage. accidental during storage, transport or product handling.
  • Another advantage is to avoid product loss on the walls of the packaging at the time of use.
  • Another advantage is, in case the dough is contained in a water soluble sachet to provide a product the packaging of which remains after use contains no trace active ingredient and whose loss in the event of opening or accidental tear is zero unlike a liquid or a gel.
  • the active ingredient is a liquid or solid pesticide, soluble or insoluble in water.
  • It can be an insecticide, a miticide, a fungicide or growth regulator.
  • a mixture can be used citric acid and a carbonate or hydrogen carbonate alkaline or alkaline earth, for example a carbonate of sodium or potassium or a calcium carbonate or a sodium hydrogencarbonate; we can use others acids than citric acid, for example ascorbic acid or adipic acid.
  • a glycol which reacts slowly with the effervescent agent and causes a release of carbon dioxide within the dough it is preferably monopropylene glycol.
  • the subject of the invention is more particularly the pesticide formulations containing containing from 20 to 50% effervescent agents.
  • the subject of the invention is in particular the formulations containing additionally from 3 to 10% of wetting agents or else the formulations containing in addition from 20 to 40% of agents wetting agents.
  • the wetting agent may be a sodium acid salt aliphatic or a lignosulfonate.
  • the subject of the invention is in particular the formulations containing between 5 and 40% mineral filler or filler organic which can optionally be substituted for wetting.
  • Mineral fillers must have absorbency sufficient to retain the constituents without desorption formulation fluids; it is preferably silica, for example silica of aerosil or zeosil type or many clays like argirec, vercoryl, or anhydrous aluminous, potassium or sodium silicates or finally sodium borate.
  • silica for example silica of aerosil or zeosil type or many clays like argirec, vercoryl, or anhydrous aluminous, potassium or sodium silicates or finally sodium borate.
  • Organic fillers can for example be chosen among celluloses, derivatives of starches or corn, urea, lactose and sugars, polyvinylpyrolidone.
  • the solvent used is very important for success of the invention, it must be a good solvent for the material active, it may for example be an aromatic solvent, such as Solvesso 200® or an isoparaffinic solvent such than Isopar V®.
  • ketone solvents such as than isophorone, acetophenone or cyclohexanone associated to various co-solvents such as n-butyl acetate, arcosolv PMA (methoxy propanol acetate), butylbenzoate or diethylphthalate.
  • the anti-foaming product can for example be Rhodorsil®.
  • Surfactants and stabilizers can be for example those used in the experimental part or still those known to be their equivalent.
  • the invention particularly relates to the formulations characterized in that the effervescent agent is a mixture of citric acid and sodium carbonate, formulations characterized in that the agent generating micropores is a glycol.
  • the active ingredient is a fungicidal, herbicidal pesticide, insecticide and more particularly for insecticides a pyrethroid selected from the group of the following products: deltamethrin, cypermethrin, alphamethrin, tralomethrin, cyalothrin, fenvalerate, cyfluthrin, flucythrenate, fluvalinate, fenpropathrin, tefluthrin, bifenthrin, acrinathrin, betacyfluthrin, taufluvalinate, lambdacyalothrin and esfenvalerate.
  • a pyrethroid selected from the group of the following products: deltamethrin, cypermethrin, alphamethrin, tralomethrin, cyalothrin, fenvalerate, cyfluthrin, flucythrenate, fluvalinate,
  • the invention particularly relates to formulations in which the pyrethroid is deltamethrin, for example those containing from 1 to 15% of deltamethrin.
  • the subject of the invention is also a method of preparation characterized in that an emulsifiable concentrate is prepared containing the active ingredient, pours it on the mixture of solid charges and knead all to obtain a homogeneous paste.
  • the active material is preformulated in the form of emulsifiable concentrate or as a suspension concentrated in oil.
  • formulations according to the invention are introduced in water-soluble sachets, which are then crimped and packaged in an overpack ensuring the protection of sachets.
  • the invention therefore also relates to the formulations as defined above packaged in a sachet soluble.
  • This sachet can in particular consist of a PVA film multi-layer or single-layer water-soluble or laminated film double layer.
  • a PVA film multi-layer or single-layer water-soluble or laminated film double layer We can cite for example the films NEDI®, EF 300 or EP 300.
  • dehydrating agent such as sulphate sodium, calcium chloride, maleic anhydride or still water-capturing solvents such as cyclohexanone or acetophenone for example.
  • the formulations thus obtained have good stability and good biological activity.
  • the pastes of the invention diluted in water giving an emulsion are preferably used in agriculture, in the treatment of crops or in the treatment animals or in public and domestic hygiene. Fields of use are those of the raw materials used.
  • compositions of the invention are prepared as follows:
  • Solid fillers must have a particle size of less than 15 ⁇ . If not, they should be micronized. They are then mixed in a Lödige type.
  • the emulsifiable concentrate is poured over the mixture of solid loads, the whole is then kneaded in a device until a homogeneous paste is obtained.
  • the paste obtained is placed in a water-soluble sachet it is then crimped.
  • the pastes of examples 1 and 2 can be packaged in water-soluble PVA sachets.
  • Outer packaging PVC coated aluminum can provide protection of these sachets.
  • Examples 12 to 17 are packaged in sachets of PVA, Nedi EF AK film.
  • INGREDIENT Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 DELTAMETHRIN 5.040 5.040 5.040 5.040 5.040 BHT 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 PHENYLSULFONATE CALCIUM 0.745 0.745 0.745 0.745 0.851 EMULSOGEN EL 1,738 1,738 1,738 1,738 1,738 1,738 1.631 ISOPHORONE 21,278 21,278 21,278 21,278 21,278 21,278 SOLVESSO 200 6.631 ARCOSOLV PMA 6.631 ANISOLE 27,909 BUTYLBENZOATE 6.631 N-BUTYL ACETATE 6.631 DIETHYLPHTHALATE 6.631 CARBONATE SODIUM 22,340 22,340 22,340 22,340 22,340 22,340 22,340
  • Example 18 The preparation of Example 18 is conditioned in PVA sachets, Nedi EF.210 film.
  • Example 19 The preparation of Example 19 is packaged in sachets of PVA, Nedi EF AK film. INGREDIENTS Ex. 18 Component.% Ex. 19 Component.% DELTAMETHRIN 98.5% 5.04 5.04 BHT 0.10 0.10 DIETHYLPHTHALATE 0.70 0.70 ACETOPHENONE 13.90 13.90 EMULSOGEN EL 1.90 1.90 SOLVESSO 200 13.76 13.76 CO 3 Na 2 15.40 15.40 CITRIC ACID ANHYDROUS 29.30 29.30 WET IS 19.90 19.90
  • the insecticidal activity of the formulations of the invention has been studied on Rhopalosiphum padi (females wingless to first and second larval stage), the host plant being the tea (stage 2 f. Florence-Aurore variety).
  • the formulations of the invention are as effective as the commercial formulation Décis ® EC 25 g / l. The formulations therefore have a excellent activity.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PCT No. PCT/FR95/00471 Sec. 371 Date Sep. 24, 1996 Sec. 102(e) Date Sep. 24, 1996 PCT Filed Apr. 12, 1995 PCT Pub. No. WO95/28082 PCT Pub. Date Oct. 26, 1995A readily, water-dispersible pesticide formulation in the form of a thick paste containing 1 to 80% by weight of the pesticide, 0.30 to 2.0% by weight of a micropore-generating agent and 30 to 50% by weight of effervescent agents the percentages being based on the total weight of the formulation.

Description

La présente invention concerne de nouvelles formulations pesticides et leur procédé de préparation.The present invention relates to new formulations pesticides and their preparation process.

L'invention a pour objet les formulations pesticides se présentant sous forme de pâtes renfermant :

  • entre 1 % et 80 % de matière active et de préférence entre 1 et 20 % de matière active pure ou en solution dans un solvant,
  • entre 20 et 50 % d'agents effervescents,
  • entre 0,30 et 2 % d'agents générateurs de micropores.
The subject of the invention is pesticide formulations in the form of pastes containing:
  • between 1% and 80% of active material and preferably between 1 and 20% of active material pure or in solution in a solvent,
  • between 20 and 50% of effervescent agents,
  • between 0.30 and 2% of micropore generating agents.

Les formulations de l'invention se présentent sous la forme d'une pâte épaisse ayant la propriété d'être effervescente et de posséder une structure microporeuse ce qui lui confère une très bonne dispersion dans l'eau.The formulations of the invention are presented under the form of a thick paste having the property of being effervescent and to have a microporous structure which gives a very good dispersion in water.

Cette pâte peut se présenter à l'intérieur d'un sachet plastique soluble à l'eau, en granulés extrudés ou en plaquettes. Les deux dernières présentations nécessitant une opération de séchage.This paste can be presented inside a sachet water-soluble plastic, in extruded granules or in platelets. The last two presentations requiring a drying operation.

Cette pâte est une composition qui possède un coefficient de viscoélasticité très faible, ce n'est pas une solution colloïdale comme un gel, mais résulte d'une absorption par un solide, d'un liquide jusqu'à saturation, la granulométrie des particules solides étant comprise entre 5 et 40 µ.This paste is a composition which has a coefficient very low viscoelasticity, this is not a solution colloidal as a gel, but results from absorption by a solid, a liquid until saturation, the particle size solid particles being between 5 and 40 μ.

La matière active est en solution dans un solvant peu volatil et les émulsifiants contenus dans ce solvant permettent à la préparation de libérer le principe actif sous forme d'une émulsion après sa dilution dans l'eau.The active ingredient is in solution in a weak solvent volatile and the emulsifiers contained in this solvent allow preparation to release the active ingredient under form of an emulsion after dilution in water.

Les formulations de l'invention possèdent une structure microporeuse facilitant leur dispersion dans l'eau au moment de leur utilisation. Cette structure est obtenue en provoquant un dégagement gazeux au sein de la pâte au moment de sa préparation. Le gaz est libéré par la réaction du générateur de micropores et de l'agent effervescent.The formulations of the invention have a structure microporous facilitating their dispersion in water at the time of their use. This structure is obtained by causing a gaseous evolution within the dough at the time of its preparation. The gas is released by the reaction of the generator micropores and the effervescent agent.

Un des avantages de l'invention est de présenter des formulations telles que des suspensions concentrées ou des concentrés émulsifiables habituellement liquides, sous la forme d'un solide ou d'une pâte.One of the advantages of the invention is to present formulations such as concentrated suspensions or usually liquid emulsifiable concentrates, under the form a solid or a paste.

Un autre avantage est d'éviter ainsi tout risque d'écoulement accidentel au cours du stockage, du transport ou de la manipulation du produit.Another advantage is to avoid any risk of leakage. accidental during storage, transport or product handling.

Un autre avantage est d'éviter les pertes de produits sur les parois des emballages au moment de l'utilisation.Another advantage is to avoid product loss on the walls of the packaging at the time of use.

Un autre avantage est, dans le cas où la pâte est contenue dans un sachet soluble dans l'eau de fournir un produit dont l'emballage restant après usage ne contient aucune trace de principe actif et dont la perte en cas d'ouverture ou de déchirure accidentelle est nulle contrairement à un liquide ou à un gel.Another advantage is, in case the dough is contained in a water soluble sachet to provide a product the packaging of which remains after use contains no trace active ingredient and whose loss in the event of opening or accidental tear is zero unlike a liquid or a gel.

La matière active est un pesticide liquide ou solide, soluble ou insoluble dans l'eau.The active ingredient is a liquid or solid pesticide, soluble or insoluble in water.

Il peut s'agir d'un insecticide, d'un acaricide, d'un fongicide ou d'un régulateur de croissance.It can be an insecticide, a miticide, a fungicide or growth regulator.

Comme agent effervescent, on peut utiliser un mélange d'acide citrique et d'un carbonate ou hydrogénocarbonate alcalin ou alcalinoterreux, par exemple un carbonate de sodium ou de potassium ou un carbonate de calcium ou un hydrogénocarbonate de sodium ; on peut utiliser d'autres acides que l'acide citrique, par exemple l'acide ascorbique ou l'acide adipique.As an effervescent agent, a mixture can be used citric acid and a carbonate or hydrogen carbonate alkaline or alkaline earth, for example a carbonate of sodium or potassium or a calcium carbonate or a sodium hydrogencarbonate; we can use others acids than citric acid, for example ascorbic acid or adipic acid.

Comme agent générateur de micropores, on peut utiliser un glycol qui réagit lentement avec l'agent effervescent et provoque un dégagement de gaz carbonique au sein de la pâte, il s'agit de préférence du monopropylène glycol.As a micropore-generating agent, it is possible to use a glycol which reacts slowly with the effervescent agent and causes a release of carbon dioxide within the dough, it is preferably monopropylene glycol.

L'invention a plus particulièrement pour objet les formulations pesticides renfermant renfermant de 20 à 50 % d'agents effervescents.The subject of the invention is more particularly the pesticide formulations containing containing from 20 to 50% effervescent agents.

L'invention a notamment pour objet les formulations renfermant en outre de 3 à 10 % d'agents mouillants ou encore les formulations renfermant en outre de 20 à 40 % d'agents mouillants.The subject of the invention is in particular the formulations containing additionally from 3 to 10% of wetting agents or else the formulations containing in addition from 20 to 40% of agents wetting agents.

L'agent mouillant peut être un sel sodique d'acide aliphatique ou un lignosulfonate.The wetting agent may be a sodium acid salt aliphatic or a lignosulfonate.

L'invention a notamment pour objet les formulations renfermant entre 5 et 40 % de charge minérale ou de charge organique pouvant éventuellement être substituée au mouillant.The subject of the invention is in particular the formulations containing between 5 and 40% mineral filler or filler organic which can optionally be substituted for wetting.

Les charges minérales doivent posséder un pouvoir absorbant suffisant pour retenir sans désorption les constituants liquides de la formulation ; il s'agit de préférence de silices, par exemple de silice de type aérosil ou zéosil ou bien d'argiles comme l'argirec, le vercoryl, ou encore de silicates alumineux, potassiques ou sodiques anhydres ou enfin du borate de sodium.Mineral fillers must have absorbency sufficient to retain the constituents without desorption formulation fluids; it is preferably silica, for example silica of aerosil or zeosil type or many clays like argirec, vercoryl, or anhydrous aluminous, potassium or sodium silicates or finally sodium borate.

Les charges organiques peuvent être par exemple choisies parmi les celluloses, les dérivés d'amidons ou de maïs, l'urée, le lactose et les sucres, la polyvinylpyrolidone.Organic fillers can for example be chosen among celluloses, derivatives of starches or corn, urea, lactose and sugars, polyvinylpyrolidone.

L'invention a plus particulièrement pour objet les formulations pesticides renfermant en outre entre

  • 0,1 et 0,5 % de produit anti-mousse,
  • 0,01 et 70 % de solvant organique,
  • 0,4 et 2 % de tensioactif,
  • 0,01 et 0,05 % de stabilisant.
A more particular subject of the invention is the pesticide formulations further comprising between
  • 0.1 and 0.5% anti-foaming product,
  • 0.01 and 70% organic solvent,
  • 0.4 and 2% surfactant,
  • 0.01 and 0.05% stabilizer.

Le solvant utilisé est très important pour la réussite de l'invention, il doit être un bon solvant de la matière active, il peut s'agir par exemple d'un solvant aromatique, comme le Solvesso 200® ou d'un solvant isoparaffinique tel que l'Isopar V®.The solvent used is very important for success of the invention, it must be a good solvent for the material active, it may for example be an aromatic solvent, such as Solvesso 200® or an isoparaffinic solvent such than Isopar V®.

Il peut s'agir également de solvants cétoniques telles que l'isophorone, l'acétophénone ou la cyclohexanone associés à différents co-solvants tels que l'acétate de n-butyle, l'arcosolv PMA (acétate de méthoxy propanol), le butylbenzoate ou encore le diéthylphtalate.They may also be ketone solvents such as than isophorone, acetophenone or cyclohexanone associated to various co-solvents such as n-butyl acetate, arcosolv PMA (methoxy propanol acetate), butylbenzoate or diethylphthalate.

Le produit anti-mousse peut être par exemple le Rhodorsil®. Les tensioactifs et les stabilisants peuvent être par exemple ceux utilisés dans la partie expérimentale ou encore ceux connus pour leur être équivalents.The anti-foaming product can for example be Rhodorsil®. Surfactants and stabilizers can be for example those used in the experimental part or still those known to be their equivalent.

L'invention a tout spécialement pour objet les formulations caractérisées en ce que l'agent effervescent est un mélange d'acide citrique et de carbonate de sodium, les formulations caractérisées en ce que l'agent générateur de micropores est un glycol. The invention particularly relates to the formulations characterized in that the effervescent agent is a mixture of citric acid and sodium carbonate, formulations characterized in that the agent generating micropores is a glycol.

Parmi les formulations préférées de l'invention, on peut citer tout spécialement les formulations caractérisées en ce que la matière active est un pesticide fongicide, herbicide, insecticide et plus particulièrement pour les insecticides un pyréthrinoïde choisi dans le groupe des produits suivants : la deltaméthrine, la cyperméthrine, l'alphaméthrine, la tralométhrine, la cyalothrine, le fenvalérate, la cyfluthrine, le flucythrénate, le fluvalinate, la fenpropathrine, la téfluthrine, la bifenthrine, l'acrinathrine, la bétacyfluthrine, le taufluvalinate, la lambdacyalothrine et l'esfenvalérate.Among the preferred formulations of the invention, it is possible to quote especially the formulations characterized in that that the active ingredient is a fungicidal, herbicidal pesticide, insecticide and more particularly for insecticides a pyrethroid selected from the group of the following products: deltamethrin, cypermethrin, alphamethrin, tralomethrin, cyalothrin, fenvalerate, cyfluthrin, flucythrenate, fluvalinate, fenpropathrin, tefluthrin, bifenthrin, acrinathrin, betacyfluthrin, taufluvalinate, lambdacyalothrin and esfenvalerate.

L'invention a tout particulièrement pour objet les formulations dans lesquelles le pyréthrinoïde est la deltaméthrine, par exemple celles renfermant de 1 à 15 % de deltaméthrine.The invention particularly relates to formulations in which the pyrethroid is deltamethrin, for example those containing from 1 to 15% of deltamethrin.

L'invention a également pour objet un procédé de préparation caractérisé en ce que l'on prépare un concentré émulsifiable renfermant le principe actif, le verse sur le mélange des charges solides et malaxe le tout pour obtenir une pâte homogène.The subject of the invention is also a method of preparation characterized in that an emulsifiable concentrate is prepared containing the active ingredient, pours it on the mixture of solid charges and knead all to obtain a homogeneous paste.

Dans un mode de réalisation préféré du procédé de l'invention, la matière active est préformulée sous forme de concentré émulsifiable ou encore sous forme de suspension concentrée dans l'huile.In a preferred embodiment of the method of the invention, the active material is preformulated in the form of emulsifiable concentrate or as a suspension concentrated in oil.

Les formulations selon l'invention sont introduites dans des sachets solubles dans l'eau, qui sont ensuite sertis et conditionnés dans un suremballage assurant la protection des sachets.The formulations according to the invention are introduced in water-soluble sachets, which are then crimped and packaged in an overpack ensuring the protection of sachets.

L'invention a donc également pour objet les formulations telles que définies ci-dessus conditionnés dans un sachet soluble.The invention therefore also relates to the formulations as defined above packaged in a sachet soluble.

Ce sachet peut être notamment constitué d'un film en PVA hydrosoluble multicouche ou monocouche ou d'un film laminé double couche. On peut citer par exemple les films NEDI ®, EF 300 ou EP 300.This sachet can in particular consist of a PVA film multi-layer or single-layer water-soluble or laminated film double layer. We can cite for example the films NEDI®, EF 300 or EP 300.

Afin d'éviter un gonflement éventuel pendant le stockage des sachets, on peut ajouter dans la composition de la pâte entre 2 et 10 % d'agent déshydratant tel que le sulfate de sodium, le chlorure de calcium, l'anhydride maléique ou encore des solvants capteurs d'eau tels que la cyclohexanone ou l'acétophénone par exemple.To avoid possible swelling during storage sachets, we can add in the composition of the dough between 2 and 10% dehydrating agent such as sulphate sodium, calcium chloride, maleic anhydride or still water-capturing solvents such as cyclohexanone or acetophenone for example.

Les formulations ainsi obtenues ont une bonne stabilité et une bonne activité biologique.The formulations thus obtained have good stability and good biological activity.

Les pâtes de l'invention diluées dans l'eau en donnant une émulsion sont utilisées de préférence en agriculture, dans le traitement des cultures ou encore dans le traitement des animaux ou en hygiène publique et domestique. Les domaines d'utilisation sont ceux des matières premières utilisées.The pastes of the invention diluted in water giving an emulsion are preferably used in agriculture, in the treatment of crops or in the treatment animals or in public and domestic hygiene. Fields of use are those of the raw materials used.

Les exemples suivants illustrent l'invention :The following examples illustrate the invention:

Les formulations de l'invention sont préparées comme suit :The formulations of the invention are prepared as follows:

A - Préparation du concentré émulsifiable de base A - Preparation of the basic emulsifiable concentrate

Les différents ingrédients, tensioactifs, solvants, matières actives, stabilisants et autres sont mélangés sous agitation jusqu'à l'obtention d'une solution.The different ingredients, surfactants, solvents, active ingredients, stabilizers and others are mixed under stirring until a solution is obtained.

B - Préparation des charges solides B - Preparation of solid charges

Les charges solides doivent avoir une granulométrie de moins de 15 µ. Si ce n'est pas le cas elles devront être micronisées. Elles sont ensuite mélangées dans un appareil de type Lödige.Solid fillers must have a particle size of less than 15 µ. If not, they should be micronized. They are then mixed in a Lödige type.

C - Préparation de la pâte C - Preparation of the dough

Le concentré émulsifiable est versé sur le mélange des charges solides, le tout est ensuite malaxé dans un appareil jusqu'à l'obtention d'une pâte homogène.The emulsifiable concentrate is poured over the mixture of solid loads, the whole is then kneaded in a device until a homogeneous paste is obtained.

D - Conditionnement de préférence D - Preference packaging

La pâte obtenue est placée dans un sachet hydrosoluble celui-ci est ensuite serti.The paste obtained is placed in a water-soluble sachet it is then crimped.

Préparation du concentré émulsifiable de basePreparation of the basic emulsifiable concentrate

On a préparé un concentré émulsifiable renfermant : Deltaméthrine 100 % 14,50 % B.H.T. 0,10 % Phénylsulfonate de CA 5,03 % Emulsogen EL 360 1,67 % Solvesso 200 78,70 % An emulsifiable concentrate containing: 100% Deltamethrin 14.50% BHT 0.10% CA phenylsulfonate 5.03% Emulsogen EL 360 1.67% Solvesso 200 78.70%

EXEMPLE 1 : on a préparé une pâte renfermant 5 % de deltaméthrine EXAMPLE 1 A dough containing 5% deltamethrin was prepared

Carbonate de sodium anhydreAnhydrous sodium carbonate 22,5 %22.5% Acide citrique anhydreAnhydrous citric acid 22,5 %22.5% Mouillant IS poudreWetting IS powder 20,0 %20.0% MonopropylèneglycolMonopropylene glycol 0,4 %0.4% Antimousse 425Defoamer 425 0,1 %0.1% Concenté émulsifiable de deltaméthrineEmulsifiable concentrate of deltamethrin 34,5 %34.5%

EXEMPLE 2 : on a préparé une pâte répondant à la formulation EXAMPLE 2 a dough corresponding to the formulation was prepared

Carbonate de sodium anhydreAnhydrous sodium carbonate 12,0 %12.0% Acide citrique anhydreAnhydrous citric acid 12,0 %12.0% Minex 10Minex 10 32,5 %32.5% Morwet D425Morwet D425 2,5 %2.5% Mouillant IS poudreWetting IS powder 6,0 %6.0% Antimousse 425Defoamer 425 0,1 %0.1% MonopropylèneglycolMonopropylene glycol 0,4 %0.4% Concenté émulsifiable de deltaméthrineEmulsifiable concentrate of deltamethrin 34,5 %34.5%

Les pâtes des exemples 1 et 2 peuvent être conditionnées dans des sachets de PVA solubles à l'eau. Un emballage extérieur en aluminium revêtu de PVC peut assurer la protection de ces sachets.The pastes of examples 1 and 2 can be packaged in water-soluble PVA sachets. Outer packaging PVC coated aluminum can provide protection of these sachets.

EXEMPLE 3 : on a préparé des granulés à 5 % de deltaméthrine renfermant EXAMPLE 3 Granules containing 5% of deltamethrin were prepared containing

Carbonate de sodium anhydreAnhydrous sodium carbonate 10,0 %10.0% Acide citrique anhydreAnhydrous citric acid 10,0 %10.0% Lactose 1 H20Lactose 1 H20 19,0 %19.0% Mouillant IS poudreWetting IS powder 26,0 %26.0% Antimousse 425Defoamer 425 0,1 %0.1% MonopropylèneglycolMonopropylene glycol 0,4 %0.4% Concenté émulsifiable de deltaméthrineEmulsifiable concentrate of deltamethrin 34,5 %34.5%

EXEMPLE 4 : on a préparé des granulés de formule EXAMPLE 4 granules of formula were prepared

Carbonate de sodium anhydreAnhydrous sodium carbonate 12,0 %12.0% Acide citrique anhydreAnhydrous citric acid 12,0 %12.0% Minex 10Minex 10 32,5 %32.5% Morwet D425Morwet D425 2,5 %2.5% Mouillant IS poudreWetting IS powder 6,0 %6.0% Antimousse 454Defoamer 454 0,1 %0.1% MonopropylèneglycolMonopropylene glycol 0,4 %0.4% Concenté émulsifiable de deltaméthrineEmulsifiable concentrate of deltamethrin 34,5 %34.5%

EXEMPLE 5 : on a préparé des plaquettes ou pastilles à 5 % de deltaméthrine de formule EXAMPLE 5 Platelets or pellets containing 5% deltamethrin of formula

Carbonate de sodium anhydreAnhydrous sodium carbonate 12,0 %12.0% Acide citrique anhydreAnhydrous citric acid 12,0 %12.0% Minex 10Minex 10 32,5 %32.5% Morwet D425Morwet D425 2,5 %2.5% Mouillant IS poudreWetting IS powder 4,5 %4.5% MonopropylèneglycolMonopropylene glycol 1,9 %1.9% Antimousse 425Defoamer 425 0,1 %0.1% Concenté émulsifiable de deltaméthrineEmulsifiable concentrate of deltamethrin 34,5 %34.5%

En opérant comme indiqué ci-dessus, on a préparé les formulations suivantes :By operating as indicated above, the following formulations:

Les préparations des exemples 6 à 11 sont conditionnées dans des sachets de PVA, film Nedi EF.210. INGREDIENT Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 DELTAMETHRINE 5,040 5,040 5,040 5,040 5,040 5,040 BHT 0,035 0,035 0,035 0,035 0,035 0,035 PHENYLSULFONATE CALCIUM 0,745 0,745 0,745 0,745 0,745 0,851 EMULSOGEN EL 1,738 1,738 1,738 1,738 1,738 1,631 ISOPHORONE 21,278 21,278 21,278 21,278 21,278 SOLVESSO 200 6,631 ARCOSOLV PMA 6,631 ANISOLE 27,909 BUTYLBENZOATE 6,631 ACETATE DE n-BUTYLE 6,631 DIETHYLPHTALATE 6,631 CARBONATE SODIUM 22,340 22,340 22,340 22,340 22,340 22,340 ACIDE CITRIQUE 22,340 22,340 22,340 22,340 22,340 22,340 MOUILLANT IS 19,853 19,853 19,853 19,853 19,853 19,853 The preparations of Examples 6 to 11 are packaged in sachets of PVA, Nedi EF.210 film. INGREDIENT Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 DELTAMETHRIN 5.040 5.040 5.040 5.040 5.040 5.040 BHT 0.035 0.035 0.035 0.035 0.035 0.035 PHENYLSULFONATE CALCIUM 0.745 0.745 0.745 0.745 0.745 0.851 EMULSOGEN EL 1,738 1,738 1,738 1,738 1,738 1.631 ISOPHORONE 21,278 21,278 21,278 21,278 21,278 SOLVESSO 200 6.631 ARCOSOLV PMA 6.631 ANISOLE 27,909 BUTYLBENZOATE 6.631 N-BUTYL ACETATE 6.631 DIETHYLPHTHALATE 6.631 CARBONATE SODIUM 22,340 22,340 22,340 22,340 22,340 22,340 CITRIC ACID 22,340 22,340 22,340 22,340 22,340 22,340 WET IS 19,853 19,853 19,853 19,853 19,853 19,853

Les préparations des exemples 12 à 17 sont conditionnées dans des sachets de PVA, film Nedi EF AK. INGREDIENT Ex.12 Ex.13 Ex.14 Ex.15 Ex.16 Ex.17 DELTAMETHRINE 5,040 5,040 5,040 5,040 5,040 5,040 BHT 0,035 0,035 0,035 0,035 0,035 0,035 PHENYLSULFONATE CALCIUM 0,745 0,745 0,745 0,745 0,745 0,851 EMULSOGEN EL 1,738 1,738 1,738 1,738 1,738 1,631 ISOPHORONE 21,278 21,278 21,278 21,278 21,278 SOLVESSO 200 6,631 ARCOSOLV PMA 6,631 ANISOLE 27,909 BUTYLBENZOATE 6,631 ACETATE DE n-BUTYLE 6,631 DIETHYLPHTALATE 6,631 CARBONATE SODIUM 22,340 22,340 22,340 22,340 22,340 22,340 ACIDE CITRIQUE 22,340 22,340 22,340 22,340 22,340 22,340 MOUILLANT IS 19,853 19,853 19,853 19,853 19,853 19,853 The preparations of Examples 12 to 17 are packaged in sachets of PVA, Nedi EF AK film. INGREDIENT Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 DELTAMETHRIN 5.040 5.040 5.040 5.040 5.040 5.040 BHT 0.035 0.035 0.035 0.035 0.035 0.035 PHENYLSULFONATE CALCIUM 0.745 0.745 0.745 0.745 0.745 0.851 EMULSOGEN EL 1,738 1,738 1,738 1,738 1,738 1.631 ISOPHORONE 21,278 21,278 21,278 21,278 21,278 SOLVESSO 200 6.631 ARCOSOLV PMA 6.631 ANISOLE 27,909 BUTYLBENZOATE 6.631 N-BUTYL ACETATE 6.631 DIETHYLPHTHALATE 6.631 CARBONATE SODIUM 22,340 22,340 22,340 22,340 22,340 22,340 CITRIC ACID 22,340 22,340 22,340 22,340 22,340 22,340 WET IS 19,853 19,853 19,853 19,853 19,853 19,853

La préparation de l'exemple 18 est conditionnée dans des sachets de PVA, film Nedi EF.210.The preparation of Example 18 is conditioned in PVA sachets, Nedi EF.210 film.

La préparation de l'exemple 19 est conditionnée dans des sachets de PVA, film Nedi EF AK. INGREDIENTS Ex. 18 Composi.% Ex. 19 Composi.% DELTAMETHRINE 98,5% 5,04 5,04 BHT 0,10 0,10 DIETHYLPHTALATE 0,70 0,70 ACETOPHENONE 13,90 13,90 EMULSOGEN EL 1,90 1,90 SOLVESSO 200 13,76 13,76 CO3Na2 15,40 15,40 ACIDE CITRIQUE ANHYDRE 29,30 29,30 MOUILLANT IS 19,90 19,90 The preparation of Example 19 is packaged in sachets of PVA, Nedi EF AK film. INGREDIENTS Ex. 18 Component.% Ex. 19 Component.% DELTAMETHRIN 98.5% 5.04 5.04 BHT 0.10 0.10 DIETHYLPHTHALATE 0.70 0.70 ACETOPHENONE 13.90 13.90 EMULSOGEN EL 1.90 1.90 SOLVESSO 200 13.76 13.76 CO 3 Na 2 15.40 15.40 CITRIC ACID ANHYDROUS 29.30 29.30 WET IS 19.90 19.90

Préparation du concentré émulsifiable de base : Preparation of the basic emulsifiable concentrate :

On a préparé un concentré émulsifiable renfermant : INGREDIENT Ex.20 Ex.21 Ex.22 Ex.23 Ex.24 DELTAMETHRINE 98,5% 14,2 14,2 14,2 14,2 14,2 BHT 0,1 0,1 0,1 0,1 0,1 PHENYLSULFONATE CALCIUM 3,5 3,5 3,5 3,5 3,5 EMULSOGEN EL 3,5 3,5 3,5 3,5 3,5 SOLVESSO 200 48,7 0 0 0 0 CYCLOHEXANONE 30,0 30,0 30,0 30,0 30,0 ARCOSOLV PMA 48,7 0 0 0 ANISOLE 0 0 0 BUTYLBENZOATE 48,7 0 0 ACETATE DE n-BUTYLE 48,7 0 DIETHYLPHTALATE 48,7 An emulsifiable concentrate containing: INGREDIENT Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 DELTAMETHRIN 98.5% 14.2 14.2 14.2 14.2 14.2 BHT 0.1 0.1 0.1 0.1 0.1 PHENYLSULFONATE CALCIUM 3.5 3.5 3.5 3.5 3.5 EMULSOGEN EL 3.5 3.5 3.5 3.5 3.5 SOLVESSO 200 48.7 0 0 0 0 CYCLOHEXANONE 30.0 30.0 30.0 30.0 30.0 ARCOSOLV PMA 48.7 0 0 0 ANISOLE 0 0 0 BUTYLBENZOATE 48.7 0 0 N-BUTYL ACETATE 48.7 0 DIETHYLPHTHALATE 48.7

Etude de stabilitéStability study

On a étudié le comportement au stockage des formulations de l'invention.We studied the storage behavior of the formulations of the invention.

Etude biologiqueBiological study

L'activité insecticide des formulations de l'invention a été étudiée sur Rhopalosiphum padi (femelles aptères au premier et second stade larvaire), la plante hôte étant le thé (stade 2 f. variété Florence-Aurore). Les formulations de l'invention sont aussi efficaces que la formulation commerciale Décis ® EC 25 g/l. Les formulations ont donc une excellente activité.The insecticidal activity of the formulations of the invention has been studied on Rhopalosiphum padi (females wingless to first and second larval stage), the host plant being the tea (stage 2 f. Florence-Aurore variety). The formulations of the invention are as effective as the commercial formulation Décis ® EC 25 g / l. The formulations therefore have a excellent activity.

Claims (16)

  1. Pesticide formulations being presented in the form of pastes containing:
    between 1% and 80% of active ingredient, pure or in solution,
    between 0 and 50% of effervescent agents,
    between 0.30 and 2% of micropore-generating agents.
  2. Pesticide formulations according to claim 1, containing from 30 to 50% of effervescent agents.
  3. Pesticide formulations according to claim 1, containing in addition 3 to 10% of wetting agents.
  4. Pesticide formulations according to claim 1, containing in addition 20 to 40% of wetting agents.
  5. Formulations according to one of claims 1 or 4, containing between 5 and 40% of a mineral filler.
  6. Pesticide formulations according to any one of claims 1 to 5, characterized in that they contain in addition between:
    0.1 and 0.5% of anti-foam product,
    0.01 and 70% of organic solvent,
    0.4 and 2% of surfactant,
    0.01 and 0.05% of stabilizing agent.
  7. Formulations according to any one of claims 1 to 6, characterized in that the effervescent agent is a mixture of citric acid and sodium carbonate.
  8. Formulations according to any one of claims 1 to 7, characterized in that the micropore-generating agent is a glycol.
  9. Formulations according to any one of claims 1 to 8, characterized in that the active ingredient is a pyrethrinoid chosen from the following group of products: deltamethrin, cypermethrin, alphamethrin, tralomethrin, cyhalothrin, fenvalerate, cyfluthrin, flucythrenate, fluvalinate, fenpropathrin, tefluthrin, bifenthrin, acrinathrin, betacyfluthrin, taufluvalinate, lambdacyalothrin and esfenvalerate.
  10. Formulations according to claim 9 in which the pyrethrinoid is deltamethrin.
  11. Formulations according to claim 10 containing from 1 to 15% of deltamethrin.
  12. Preparation process for formulations according to any one of claims 1 to 11, characterized in that an emulsifiable concentrate is prepared containing the active ingredient, it is poured over the mixture of solid fillers and the whole is mixed in order to obtain a homogeneous paste.
  13. Formulations according to any one of claims 1 to 11, characterized in that the active ingredient is pre-formulated in the form of an emulsifiable concentrate.
  14. Formulations according to any one of claims 1 to 11, characterized in that the active ingredient is pre-formulated in the form of a concentrated suspension in oil.
  15. Formulations according to any one of claims 1 to 14, characterized in that they are packaged in a soluble sachet.
  16. Formulations according to any one of claims 1 to 15, characterized in that they contain in addition 2 to 10% of a dehydrating agent.
EP95917381A 1994-04-14 1995-04-12 Novel pesticide compositions and method of preparation Expired - Lifetime EP0755184B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9404440 1994-04-14
FR9404440A FR2718610B1 (en) 1994-04-14 1994-04-14 New pesticide formulations and their preparation process.
PCT/FR1995/000471 WO1995028082A1 (en) 1994-04-14 1995-04-12 Novel pesticide compositions and method of preparation

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EP0755184A1 EP0755184A1 (en) 1997-01-29
EP0755184B1 true EP0755184B1 (en) 1998-08-12

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CN101455196B (en) * 2008-12-23 2012-09-05 中国人民解放军海军医学研究所 Pesticide effervescence combination and preparation method thereof
CN101913942A (en) * 2009-07-10 2010-12-15 深圳市朗钛生物科技有限公司 Agricultural effervescent granules and preparation method and application thereof
CN102823589B (en) * 2012-09-24 2014-06-04 发事达(南通)化工有限公司 Pesticide water effervescent dispersible tablet and preparation method thereof
US10684261B2 (en) 2016-04-01 2020-06-16 General Electric Company Ultrasonic bar and tube end testing with linear axis robot
UA128080C2 (en) * 2016-12-07 2024-04-03 Адама Махтешім Лтд. A stable, self-dispersible, low foaming solid pesticide formulation

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DE935336C (en) * 1950-12-16 1955-11-17 Hans Dipl-Chem Bremer Basis for ointment-like or sticky pest repellants or pesticides
JPS554336A (en) * 1978-06-23 1980-01-12 Kyoritsu Sanitarii Kk Solid or pasty emulsion composition
ZW1682A1 (en) * 1981-02-09 1983-08-31 Aeci Ltd Insecticidal composition
JPH0635362B2 (en) * 1985-08-19 1994-05-11 日本農薬株式会社 Stable paste pesticide application
US4765984A (en) * 1986-01-22 1988-08-23 Colgate-Palmolive Company Stable single unit dose oral product
ES2055894T3 (en) * 1989-04-07 1994-09-01 Ciba Geigy Ag CONCENTRATES OF PESTICIDED ACTIVE SUBSTANCES AND THEIR PREPARATION.
MA22221A1 (en) * 1990-07-18 1992-04-01 Rhone Poulenc Agrochimie GEL FORMULATIONS FOR USE IN TOXIC PRODUCT PACKAGING SYSTEMS
EP0480679B1 (en) * 1990-10-11 1996-09-18 Sumitomo Chemical Company Limited Pesticidal composition
MA22490A1 (en) * 1991-04-02 1992-12-31 Rhone Poulenc Agrochimie INSECTICIDE COMPOSITION AND INSECTICIDE UNIT
JP3283048B2 (en) * 1991-09-26 2002-05-20 北興化学工業株式会社 Foaming pesticide formulation for water application
FR2686320B1 (en) * 1991-11-21 1996-12-13 Rhone Poulenc Agrochimie AGROCHEMICAL COMPOSITION EFFERVESCENT IN THE PULVERULENT STATE IN A WATER-SOLUBLE OR WATER-DISPERSABLE BAG.
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US5266218A (en) * 1993-04-15 1993-11-30 Betz Laboratories, Inc. Gelled biocidal treatments

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ATE169450T1 (en) 1998-08-15
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AU2347395A (en) 1995-11-10
BR9507383A (en) 1997-09-23
PL316787A1 (en) 1997-02-17
FR2718610B1 (en) 1996-06-07
DK0755184T3 (en) 1999-05-10
HUT75258A (en) 1997-05-28
HU9602804D0 (en) 1996-11-28
US5945113A (en) 1999-08-31
EP0755184A1 (en) 1997-01-29
AU679372B2 (en) 1997-06-26
KR970701991A (en) 1997-05-13
CN1146135A (en) 1997-03-26
DE69504050T2 (en) 1999-03-11
WO1995028082A1 (en) 1995-10-26
DE69504050D1 (en) 1998-09-17
JPH09512001A (en) 1997-12-02
TW312610B (en) 1997-08-11
FR2718610A1 (en) 1995-10-20
ZA952845B (en) 1996-04-09

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